Composition containing n-(n-butyl) thiophosphoric triamide adducts and reaction products

ABSTRACT

Reaction products and methods for making and using such reaction products are provided. For example, a reaction product comprising an adduct formed from urea, formaldehyde, and a urease inhibitor is described, which can be provided in various forms. For example, such a reaction product can be in the form of a solid or solution. Such a reaction product can also be combined with one or more additional components, including but not limited to, additional urease inhibitor and/or a nitrogen-based fertilizer composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/196,781 filed Jul. 24, 2015, herein incorporated by reference in itsentirety.

FIELD OF THE DISCLOSURE

The present subject matter relates generally to compositions comprisingurease inhibitors and to methods of preparing and using suchcompositions.

BACKGROUND

Fertilizers have been used for some time to provide nitrogen to thesoil. The most widely used and agriculturally important nitrogenfertilizer is urea, CO(NH₂)₂. Most of the urea currently produced isused as a fertilizer in its granular (or prilled) form. Afterapplication of urea to soil, it is readily hydrolyzed to yield ammoniaand carbon dioxide. This process is catalyzed by the enzyme urease,which is produced by some bacteria and fungi that may be present in thesoil. The gaseous products formed by the hydrolysis reaction (i.e.,ammonia and carbon dioxide) can volatilize to the atmosphere and thus,substantial losses from the total amount of the nitrogen applied to thesoil can occur.

Attempts to reduce losses of applied nitrogen have utilized ureaseinhibitors and/or nitrification inhibitors as additives to thefertilizer. Urease inhibitors are compounds capable of inhibiting thecatalytic activity of the urease enzyme on urea in the soil.Nitrification inhibitors are compounds capable of inhibiting thebacterial oxidation of ammonium to nitrate in the soil. Ureaseinhibitors and nitrification inhibitors can be associated withfertilizers in various ways. For example, they can be coated ontofertilizer granules or mixed into fertilizer matrices. A number ofgranulation methods are known, including falling curtain,spherudization-agglomeration drum granulation, prilling and fluid bedgranulation technologies.

Examples of urease inhibitors are the thiophosphoric triamide compoundsdisclosed in U.S. Pat. No. 4,530,714 to Kolc et al., which isincorporated herein by reference. The disclosed thiophosphoric triamidecompounds include N-(n-butyl) thiophosphoric triamide (NBPT), the mostdeveloped representative of this class of compounds. When incorporatedinto a urea-containing fertilizer, NBPT reduces the rate at which ureais hydrolyzed in the soil to ammonia. The benefits realized as a resultof the delayed urea hydrolysis include the following: (1) nutrientnitrogen is available to the plant over a longer period of time; (2)excessive build-up of ammonia in the soil following the application ofthe urea-containing fertilizer is avoided; (3) the potential fornitrogen loss through ammonia volatilization is reduced; (4) thepotential for damage by high levels of ammonia to seedlings and youngplants is reduced; (5) plant uptake of nitrogen is increased; and (6) anincrease in crop yields is attained. NBPT is commercially available foruse in agriculture and is marketed in such products as the AGROTAIN®nitrogen stabilizer product line.

Industrial grade NBPT is a solid, waxy compound, and decomposes by theaction of water, acid and/or elevated temperature. In particular, NBPTis believed to degrade at elevated temperatures into compounds that maynot provide the desired inhibitory effects on the urease enzyme.Accordingly, its combination with other solid materials to provide amaterial capable of inhibiting urease, particularly via granulation withurea (which generally employs heat) can be challenging. As such, thereis a need for urease inhibitor-containing compositions that can becombined with urea, desirably using current urea manufacturingpractices, so as to produce fertilizer compositions that provideeffective urease

SUMMARY OF THE INVENTION

As disclosed herein, compositions comprising urease inhibitors areprovided and methods for making such. Such compositions generallycomprise a reaction product between a urease inhibitor (e.g.,N-(n-butyl) thiophosphoric triamide, NBPT), urea, and formaldehyde. Suchreaction products can be characterized as adducts, as the productsarising from the reaction retain at least portions of two or more of thereactants (i.e., urease inhibitor, urea, and/or formaldehyde).Compositions arising from such reactions, comprising the disclosedreaction products, can be provided independently and can, in certainembodiments, be combined with other components. For example, suchadduct-containing compositions can be combined with fertilizer materialscomprising nitrogen sources, including but not limited to, urea,ammonia, ammonium nitrate, and combinations thereof. Advantageously,adduct-containing compositions disclosed herein, alone or in combinationwith one or more nitrogen sources, can provide fertilizers that exhibitsubstantial urease inhibitory effects and can thus be characterized bylow ammonia volatilization losses in use (i.e., upon application tosoil).

In one aspect, the present disclosure provides a composition comprisingan adduct of NBPT, urea, and formaldehyde. In another aspect, thedisclosure provides a composition comprising an adduct of NBPT, urea,and formaldehyde, and one or more materials selected from the groupconsisting of free NBPT, free formaldehyde, urea formaldehyde polymer(UFP), water, and combinations thereof. In a further aspect, thedisclosure provides a composition comprising an adduct of NBPT, urea,and formaldehyde, wherein the composition comprises substantially nodicyandiamide. In a still further aspect, the disclosure provides acomposition comprising one or more adducts of NBPT), urea, andformaldehyde, wherein the one or more adducts are represented by thefollowing structures:

The compositions provided herein can, in some embodiments, be in theform of a solution of the adduct (e.g., with an organic solvent, such asthose disclosed herein below). In certain embodiments, the compositionis a synergistic mixture of free NBPT and the adduct. The disclosedcompositions can, in some embodiments, comprise substantially nodicyandiamide (DCD). In some compositions, at least a portion (includingall) of the urea and formaldehyde are in the form of a urea formaldehydereaction product comprising dimethylolurea.

In another aspect, the present disclosure provides a fertilizercomposition comprising urea and an adduct of NBPT, urea, andformaldehyde. Any of the compositions comprising an adduct of NBPT,urea, and formaldehyde as disclosed herein can be used in suchfertilizer compositions. The fertilizer compositions can, in certainembodiments, comprise a significant amount of urea, e.g., at least about90% by weight urea, at least about 95% by weight urea, at least about98% by weight urea, at least about 99% by weight urea, or at least about99.5% by weight urea.

In a further aspect, the present disclosure provides a method of forminga fertilizer composition, the method comprising combining a compositioncomprising an adduct of NBPT, urea, and formaldehyde as disclosed hereinwith a fertilizer material. The method can, in certain embodiments,comprise mixing the adduct-containing composition with solid particlesof the fertilizer material and, in other embodiments, can comprisemixing the adduct-containing composition with a molten stream of thefertilizer material. In some embodiments, the method can furthercomprise combining free NBPT with one or both of the fertilizer materialand the adduct-containing composition.

In another aspect, the disclosure provides a method of making a ureaseinhibiting fertilizer, the method comprising combining urea,formaldehyde, and NBPT such that an excess of urea is present, to forman adduct of NBPT, urea, and formaldehyde, which adduct remainsincorporated into the remaining urea. In some embodiments, the urea andformaldehyde are in the form of a urea formaldehyde reaction productcomprising dimethylolurea.

In a further aspect, the present disclosure provides a method ofreducing hydrolysis of urea to ammonia in soil, comprising applying acomposition comprising an adduct of NBPT, urea, and formaldehyde to thesoil. Such methods can comprise combining a nitrogen source with thecomposition prior to said applying, applying the composition to the soilfollowing application of a nitrogen source to the soil, or applying thecomposition to the soil prior to application of a nitrogen source to thesoil.

In a still further aspect, the disclosure provides a method ofincorporating an adduct of NBPT, urea, and formaldehyde into moltenurea, comprising combining such an adduct (e.g., including, but notlimited to, the adduct in the form of an adduct-containing composition)with molten urea. Additionally, the disclosure provides a method offorming an adduct of NBPT, urea, and formaldehyde, comprising contactingNBPT with a molten urea stream comprising formaldehyde and/or reactionproducts of urea and formaldehyde.

In one aspect, the disclosure specifically provides a compositioncomprising a mixture of: an adduct of N-(n-butyl)thiophosphoric triamide(NBPT), urea, and formaldehyde; and free NBPT. The disclosure furtherprovides a fertilizer composition comprising urea and such acomposition. It additionally provides a method of forming a fertilizercomposition, the method comprising contacting a fertilizer material withsuch a composition and also a method of reducing hydrolysis of urea toammonia in soil, comprising applying such a composition to the soil.

BRIEF DESCRIPTION OF THE DRAWINGS

In order to provide an understanding of embodiments of the invention,reference is made to the appended figures. These figures are exemplaryonly, and should not be construed as limiting the invention.

FIG. 1 is a plot of the effect of various urease inhibitors on ammoniavolatilization (measured in ppm); and

FIG. 2 is a plot of cumulative N loss (measured in %) from urea andurease inhibitor-treated ureas.

DETAILED DESCRIPTION OF THE INVENTION

It is noted here that as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referenceunless the context clearly dictates otherwise. All percentages, partsand ratios are based upon the total weight of the compositions of thepresent invention, unless otherwise specified. All such weights as theypertain to listed ingredients are based on the active level and,therefore do not include solvents or by-products that may be included incommercially available materials, unless otherwise specified. The term“weight percent” may be denoted as “wt. %” herein. All molecular weightsas used herein are weight average molecular weights expressed asgrams/mole, unless otherwise specified.

According to the present disclosure, compositions exhibiting effectiveurease inhibition and methods of producing such compositions areprovided. It was surprisingly formed that, as higher amounts of ureaseinhibitor were added to mixtures of urea and formaldehyde, the amount offree urease inhibitor present in the final product mixture did not scaleaccordingly. Subsequently, it was determined that at least a portion ofthe urease inhibitor added to the urea and formaldehyde was reactingunder the conditions to which it was subjected to form an adductcomprising the urease inhibitor (thus decreasing the concentration offree urease inhibitor in the final product mixture). Such reactionproducts and compositions derived therefrom are described in furtherdetail herein.

In particular, reaction products comprising adducts formed from one ormore urease inhibitors with urea and/or formaldehyde are provided. Suchreaction products can be provided as-formed, can be purified to isolateone or more components therefrom, or can be provided in combination withone or more other components, such as additional urease inhibitor or afertilizer composition, e.g., in the form of a nitrogen sourceincluding, but not limited to, a urea source. The compositions disclosedherein can, in some embodiments, exhibit novel, slow-release of the oneor more urease inhibitors.

As used herein, the term “urease inhibitor” refers to any compound thatreduces, inhibits, or otherwise slows down the conversion of urea toammonium (NH₄ ⁺) in soil. Exemplary urease inhibitors includethiophosphoric triamides and phosphoric triamides of the general formula(I)

X═P(NH₂)₂NR¹R²   (I)

where X=oxygen or sulfur, and R¹ and R² are independently selected fromhydrogen, C₁-C₁₂ alkyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, C₂-C₁₂ alkenyl,C₂-C₁₂ alkynyl, C₅-C₁₄ heteroaryl, C₁-C₁₄ heteroalkyl, C₂-C₁₄heteroalkenyl, C₂-C₁₄ heteroalkynyl, or C₃-C₁₂ cycloheteroalkyl groups.

In certain embodiments, urease inhibitors are N-(alkyl) thiophosphorictriamide urease inhibitors as described in U.S. Pat. No. 4,530,714 toKolc et al., which is incorporated herein by reference. Particularillustrative urease inhibitors can include, but are not limited to,N-(n-butyl)thiophosphoric triamide, N-(n-butyl)phosphoric triamide,thiophosphoryl triamide, phenyl phosphorodiamidate, cyclohexylphosphoric triamide, cyclohexyl thiophosphoric triamide, phosphorictriamide, hydroquinone, p-benzoquinone, hexamidocyclotriphosphazene,thiopyridines, thiopyrimidines, thiopyridine-N-oxides,N,N-dihalo-2-imidazolidinone, N-halo-2-oxazolidinone, derivativesthereof, or any combination thereof. Other examples of urease inhibitorsinclude phenylphosphorodiamidate (PPD/PPDA), hydroquinone,N-(2-nitrophenyl) phosphoric acid triamide (2-NPT), ammoniumthiosulphate (ATS) and organo-phosphorous analogs of urea, which areeffective inhibitors of urease activity (see e.g. Kiss and Simihaian,Improving Efficiency of Urea Fertilizers by Inhibition of Soil UreaseActivity. Kluwer Academic Publishers, Dordrecht, The Netherlands, 2002;Watson, Urease inhibitors. IFA International Workshop onEnhanced-Efficiency Fertilizers, Frankfurt. International FertilizerIndustry Association, Paris, France 2005).

In particular embodiments, the urease inhibitor can be or can includeN-(n-butyl) thiophosphoric triamide (NBPT). The preparation ofphosphoramide urease inhibitors such as NBPT can be accomplished, forexample, by known methods starting from thiophosphoryl chloride, primaryor secondary amines and ammonia, as described, for example, in U.S. Pat.No. 5,770,771, which is incorporated herein by reference. In a firststep, thiophosphoryl chloride is reacted with one equivalent of aprimary or secondary amine in the presence of a base, and the product issubsequently reacted with an excess of ammonia to give the end product.Other methods include those described in U.S. Pat. No. 8,075,659, whichis incorporated herein by reference, where thiophosphoryl chloride isreacted with a primary and/or secondary amine and subsequently withammonia. However this method can result in mixtures. Accordingly, whenN-(n-butyl)thiophosphoric triamide (NBPT) or other urease inhibitors areused, it should be understood that this refers not only to the ureaseinhibitor in its pure form, but also to various commercial/industrialgrades of the compound, which can contain up to 50 percent (or less),preferably not more than 20 percent, of impurities, depending on themethod of synthesis and purification scheme(s), if any, employed in theproduction thereof. Combinations of urease inhibitors, for example usingmixtures of NBPT and other alkyl-substituted thiophosphoric triamides,are known.

Representative grades of urease inhibitor may contain up to about 50 wt.%, about 40% about 30%, about 20% about 19 wt. %, about 18 wt. %, about17 wt. %, about 16 wt. %, about 15 wt. %, about 14 wt. %, about 13 wt.%, about 12 wt. %, about 11 wt. %, 10 wt. %, about 9 wt. %, about 8 wt.%, about 7 wt. %, about 6 wt. % about 5 wt. %, about 4 wt. %, about 3wt. %, about 2 wt. %, or about 1 wt. % impurities, depending on themethod of synthesis and purification scheme(s), if any, employed in theproduction of the urease inhibitor. A typical impurity in NBPT isPO(NH₂)₃ which can catalyze the decomposition of NBPT under aqueousconditions. Thus in some embodiments, the urease inhibitor used is about80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%,about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%,about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about99.6%, about 99.7%, about 99.8%, or about 99.9% pure.

For simplicity, the invention may be described in relation toembodiments wherein NBPT is the urease inhibitor. Description of theinvention in terms wherein NBPT is the urease inhibitor should not beviewed as necessarily excluding the use of other urease inhibitors, orcombinations of urease inhibitors, unless expressly noted.

The urea used to produce the adducts disclosed herein can be in variousforms. For example, the urea can be a solid in the form of prills,flakes, granules, and the like, and/or a solution, such as an aqueoussolution, and/or in the form of molten urea. At least a portion of theurea can be in the form of animal waste. Both urea and combinedurea-formaldehyde products can be used according to the presentdisclosure. Illustrative urea-formaldehyde products can include, but arenot limited to, urea-formaldehyde concentrate (“UFC”) andurea-formaldehyde polymers (“UFP”). These types of products can be asdiscussed and described in U.S. Pat. Nos. 5,362,842 and 5,389,716 toGraves et al., for example, which are incorporated herein by reference.Any form of urea or urea in combination with formaldehyde can be used tomake a UFP. Examples of solid UFP include PERGOPAK M® 2, available fromAlbemarle Corporation and NITAMIN 36S, available from Koch AgronomicServices, LLC. Any of these urea sources can be used alone or in anycombination to prepare the reaction product disclosed herein.

As referenced hereinabove, in some embodiments, the formaldehyde used asa reagent to produce the reaction products disclosed herein can beprovided in combination with the urea (e.g., in the form of a mixture orpolymer with urea). In such embodiments, additional formaldehyde neednot be added to form the desired adduct, although the disclosure is notlimited thereto and it is possible to add additional formaldehyde tosuch urea-formaldehyde products.

In some embodiments, formaldehyde is intentionally added as a reagent toprepare the reaction products disclosed herein, and the formaldehyde canbe in various forms. For example, paraform (solid, polymerizedformaldehyde) and/or formalin solutions (aqueous solutions offormaldehyde, sometimes with methanol, in about 10 wt. %, about 20 wt.%, about 37 wt. %, about 40 wt. %, or about 50 wt. %, based on theweight of the formalin solution) are commonly used forms offormaldehyde. In some embodiments, the formaldehyde can be an aqueoussolution having a concentration of formaldehyde ranging from about 10wt. % to about 50 wt. % based on total weight of the aqueous solution.Formaldehyde gas can also be used. Formaldehyde substituted in part orin whole with substituted aldehydes such as acet aldehyde and/orpropylaldehyde can also be used as the source of formaldehyde. Any ofthese forms of formaldehyde sources can be used alone or in anycombination to prepare the reaction product described herein.

The method of preparing the reaction product disclosed herein can vary.Generally, NBPT is conibined with, mixed, or otherwise contacted withurea and formaldehyde. Accordingly, in some embodiments, the disclosureprovides a method for making an adduct, comprising combining urea,formaldehyde, and NBPT such that at least one adduct is formed. Forexample, at least a portion of the NBPT can react with at least aportion of the urea and/or at least a portion of the formaldehyde toform one or more structurally different adducts, as will be describedfurther hereinafter.

The reactants (i.e., urea, formaldehyde, and NBPT) can be combined withone another in any order or sequence. For example, in one embodiment,urea and formaldehyde are first combined and NBPT is added thereto. Inanother embodiment, urea and a urea formaldehyde product (e.g., ureaformaldehyde concentrate or urea-formaldehyde polymer) are combined andNBPT is added thereto. In a further embodiment, a urea formaldehydeproduct and formaldehyde are combined and NBPT is added thereto. In astill further embodiment, urea and NBPT are combined and formaldehyde ora urea formaldehyde product is added thereto. Additionally, in certainembodiments, other components can be included at any of these stages,alone, or in combination with the urea, formaldehyde, or NBPT. Forexample, in some embodiments, a nitrification inhibitor (such as thosedisclosed herein below) can be combined with one or more of thecomponents, e.g., including but not limited to, embodiments wherein thenitrification inhibitor is combined with NBPT and this mixture iscombined with the other components.

In these various embodiments, the form of the NBPT added can vary. Forexample, the NBPT can be used in molten liquid form, in solution form,or in suspension/dispersion form. Similarly, the form of the materialwith which the NBPT is combined (i.e., the urea/formaldehyde mixture,the urea/urea formaldehyde product mixture, or the urea formaldehydeproduct/formaldehyde mixture) can vary. For example, in someembodiments, the material with which the NBPT is combined can be insolution form, can be in dispersion/suspension form, or can be in theform of a molten urea liquid. In either case, the form of the NBPT,urea, and formaldehyde should allow for a high degree of contact betweenthe reagents to facilitate the reaction and formation of adducts. Themost preferred form of NBPT is a solution or suspension/dispersion. Themost preferred form of urea/formaldehyde mixture, urea/urea formaldehydeproduct mixture, urea formaldehyde product/formaldehyde mixture issolution or molten urea liquid containing the formaldehyde. In anotherembodiment that employs a MAP, DAP, or AMS catalyst to facilitate thereaction, the form of urea/formaldehyde mixture, urea/urea formaldehydeproduct mixture, urea formaldehyde product/formaldehyde mixture can be asolid (i.e. urea granule) and form of NBPT a solution

Where solvents are used at any stage of the combining process, thesolvents employed are generally those sufficient to solubilize one ormore of the NBPT, urea, and/or formaldehyde. Suitable solvents caninclude, for example, water (including aqueous buffers), N-alkyl2-pyrrolidones (e.g., N-methyl pyrrolidone), glycols and glycolderivatives, ethyl acetate, propylene glycol, benzyl alcohol, andcombinations thereof. Representative solvents known to solubilize NBPTinclude, but are not limited to, those solvents described in U.S. Pat.Nos. 5,352,265 and 5,364,438 to Weston, U.S. Pat. No. 5,698,003 toOmilinsky et al., U.S. Pat. Nos.8,048,189 and 8,888,886 to Whitehurst etal., WO2014/100561 to Ortiz-Suarez et al., WO2014/055132 to McNight etal., WO2014/028775 and WO2014/028767 to Gabrielson et al., and EP2032589to Cigler, which are incorporated herein by reference. In certainembodiments, the solvent, or mixture of solvents, employed to combinethe components can be selected from the group consisting of water(including buffered solutions, e.g., phosphate buffered solutions),glycols (e.g., propylene glycol), glycol derivatives and protectedglycols (e.g., glycerol including protected glycerols such asisopropylidine glycerol, glycol ethers e.g. monoalkyl glycol ethers,dialkyl glycol ethers), acetonitrile, DMSO, alkanolamines (e.g.,triethanolamine, diethanolamine, monoethanolamine, alkyldiethanolamines,dialkylmonoethanolamines, wherein the alkyl group can consist of methyl,ethyl, propyl, or any branched or unbranched alkyl chain), alkylsulfones(e.g., sulfolane), alkyl amides (e.g., N-methylpyrrolidone,N-ethylpyrrolidone, dimethylformamide, or any non-cyclic amide),monoalcohols (e.g., methanol, ethanol, propanol, isopropanol, benzylalcohol), dibasic esters and derivatives thereof, alkylene carbonates(e.g., ethylene carbonate, propylene carbonate), monobasic esters (e.g.,ethyl lactate, ethyl acetate), carboxylic acids (e.g., maleic acid,oleic acid, itaconic acid, acrylic acid, methacrylic acid), glycolesters, and/or surfactants (e.g. alkylbenzenesulfonates, ligninsulfonates, alkylphenol ethoxylates, polyalkoxylated amines) andcombinations thereof. Further co-solvents, including but not limited to,liquid amides, 2-pyrrolidone, N-alkyl 2-pyrrolidones, and non-ionicsurfactants (e.g., alkylaryl polyether alcohols) can be used in certainembodiments.

Various other additives that do not negatively impact the formation ofthe adducts disclosed herein can be included in the reaction mixture(i.e., urease, inhibitor(s), urea, formaldehyde, and optionalsolvent(s)). For example, components (e.g., impurities) that aregenerally present in urea and/or formaldehyde are commonly incorporatedin the reaction mixture. In some embodiments, components that aredesirably included in the final product can be incorporated into thereaction mixture (e.g., dyes, as described in further detail below).

In certain embodiments, monoammonium phosphate (MAP), diammoniumphosphate (DAP), and/or ammonium sulfate (AMS) can be used to promotethe formation of adducts. Although not intended to be limiting, it isbelieved that MAP, DAP, or AMS can function as catalysts to facilitatethe formation of the adducts disclosed herein. In some embodiments, itmay be possible, by including MAP, DAP, and/or AMS (and/or othercatalysts), to reduce the reaction time and/or to conduct the reactionat lower temperatures than would otherwise be required to form theadducts. In certain embodiments, mixing granules of NBPT-treated ureawith granules of MAP, DAP or AMS also accelerates formation of theadducts disclosed herein as compared with embodiments wherein nocatalyst is employed. In some embodiments, the use of a particularcatalyst may have an effect on the amount and/or type(s) of variousadducts formed during the reaction.

Adduct formation can be conducted at various pH values, and in someembodiments, it may be desirable to adjust the pH of the reactionmixture (e.g., by adding acid and/or base). Representative acidsinclude, but are not limited to, solutions of mineral acids such ashydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, andcombinations thereof. Exemplary bases include, but are not limited to,solutions of ammonia, amines (e.g., primary, secondary and tertiaryamines and polyamines), sodium hydroxide, potassium hydroxide, andcombinations thereof. In some embodiments, it may be desirable to employa buffer solution to control the pH of the reaction mixture.Representative buffer solutions include, but are not limited to,solutions of triethanolamine, sodium borate, potassium bicarbonate,sodium carbonate, and combinations thereof.

The conditions under which the NBPT, urea, and formaldehyde (andoptionally, other additives) are combined can vary. For example, thereaction can be conducted at various temperatures, e.g., ranging fromambient temperature (about 25° C.) to elevated temperatures (above 25°C.). In certain embodiments, the temperature at which the reaction isconducted is at least about 50° C., at least about 60° C., at leastabout 70° C., at least about 80° C., at least about 90° C., or at leastabout 100° C., such as about 20° C. to about 150° C.

Advantageously, in some embodiments, the reaction product can beprepared under conditions of conventional urea manufacturing (asdescribed, for example, in Jozeef Meesen, Ullman's Encyclopedia ofIndustrial Chemistry (2012), vol. 37, pages 657-695, which isincorporated herein by reference). Such urea manufacturing conditionsgenerally include temperatures at which urea is in molten form, e.g.,temperatures of about 130° C. to about 135° C. For example, in suchembodiments, the NBPT can be added to a molten mixture of urea andformaldehyde (or urea and urea-formaldehyde (i.e., UF, UFC or UFP)). Themixture can be combined and then cooled to provide a reaction productcomprising the reaction product, i.e., adduct of NBPT, urea, andformaldehyde. For example, the composition can be cooled by subjectingthe reaction mixture to typical urea pastillation, prilling orgranulation processes (e.g., fluidized bed granulation, drumgranulation, sprouted bed granulation, and the like), which generallycomprise a cooling step following formation of pastilles, prills and/orgranules. Generally, the drying process provides the reaction product inthe form of a solid material (e.g., a pastillated, granular or prilledsolid).

The NBPT, urea, and formaldehyde (i.e., the reaction mixture) can bemaintained together under the reaction conditions for various periods oftime. For example, in some embodiments, the reaction can be conductedwithin a relatively short period (e.g., on the order of minutes, e.g.,about 30 seconds to about 30 minutes, about 1 to about 20 minutes, orabout 1 to about 10 minutes. In some embodiments, the reaction may beconducted for about 1 minute or longer, about 2 minutes or longer, about5 minutes or longer, about 10 minutes or longer, about 15 minutes orlonger, or about 20 minutes or longer. In certain embodiments, thereaction can be conducted for about 2 hours or less, about 1 hour orless, about 30 minutes or less, about 25 minutes or less, about 20minutes or less, about 15 minutes or less, or about 10 minutes or less.In some embodiments, the components can be reacted together for asomewhat longer period, e.g., for a period of about 2 hours or longer,about 4 hours or longer, about 6 hours or longer, about 8 hours orlonger, about 10 hours or longer, about 12 hours or longer, about 14hours or loner, about 16 hours or longer, about 18 hours or longer,about 20 hours or longer, about 22 hours or longer, or about 24 hours orlonger. In some embodiments, the reaction time is about 2 hours to about48 hours, such as about 4 hours to about 36 hours.

In certain embodiments, the amount of time for which the reactionconducted may be that amount of time required to convert a givenpercentage of NBPT in the reaction mixture to adduct form. For example,in one embodiment, the reaction mixture is reacted to about 10% or lessfree (i.e., unreacted) NBPT by weight, based on total NBPT added to thereaction mixture or to about 5% or less free NBPT by weight, based ontotal NBPT added to the reaction mixture. In another embodiment, thereaction mixture is reacted to about 40% or less free (i.e. unreacted)NBPT by weight, based on the total NBPT added to the reaction mixture,or to about 30% or less free NBPT by weight, based on total NBPT addedto the reaction mixture, or to about 20% or less free NBPT by weight,based on total NBPT added to the reaction mixture. In yet anotherembodiment, the reaction mixture is reacted to about 2% or less freeNBPT by weight, based on total NBPT added to the reaction mixture, or toabout 1% or less free NBPT by weight, based on total NBPT added to thereaction mixture, or to about 0.1% or less free NBPT by weight, based ontotal NBPT added to the reaction mixture. In a further embodiment, thereaction mixture is reacted to about 50% (i.e. unreacted) NBPT byweight, based on the total NBPT added to the reaction mixture to createa 1:1 wt. % adduct:free NBPT product (as measured by phosphorouscontent). In yet a further embodiment, the reaction mixture is reactedto create a weight ratio of adduct:free NBPT product in the range fromabout 4:1 to 1:4 (as measured by phosphorous content), including 3:1 to1:3, 2:1 to 1:2, and a 1:1. Accordingly, in some embodiments, the methodof producing an adduct as described herein further comprises monitoringthe amount of free NBPT remaining over the course of the reaction andevaluating the completeness of reaction based on the amount of free NBPTin comparison to the desired maximum content of free NBPT by weight tobe included in the reaction product.

It is noted that the particular reaction components may affect thereaction conditions required to produce the reaction product. Forexample, reaction of components in one solvent may be more efficientthan reaction of those components in a different solvent and it isunderstood that, accordingly, less time and/or lower temperature may berequired for adduct formation in the former case. Also, where a catalystis employed, less time and/or lower temperature may be required foradduct formation. It is also noted that, in some embodiments, employingdifferent reaction conditions can have an effect on the amount and/ortype(s) of various adducts formed during the reaction.

The reaction products provided according to the methods disclosedhereinabove can comprise one or a plurality of structurally differentadducts. For example, a given reaction product can comprise at least oneadduct, at least two different adducts, at least three differentadducts, at least four different adducts, at least five differentadducts, at least ten different adducts, at least twenty-five differentadducts, at least about fifty different adducts, or at least about onehundred different adducts. The adducts may be in the form of discretecompounds, oligomers, polymers, and combinations thereof. The overallamount of adduct formed can vary and, likewise, the amount of eachdifferent adduct (where more than one adduct is present in thecomposition) can vary.

Certain representative adducts that have been identified in reactionproducts, based on reactions between urea, formaldehyde, and NBPT, areas follows (wherein the reference to these adducts as “Adduct 1,”“Adduct 2,” and “Adduct 3” are arbitrary names chosen to distinguishthem from one another and from other adducts that may be present invarious reaction products):

The reaction product can comprise various other components in additionto the adduct(s). It is to be understood that other components that maybe present in the reaction product can be a result of the specificmethod used to produce the reaction product and, particularly, of theamount of each reactant included in the reaction mixture. For example,where the reaction conditions are such that there is an excess of one ortwo reactants, the reaction product may comprise free reactant (i.e.,reactant which is not incorporated into an adduct). In variousembodiments, the reaction product can comprise at least some percent byweight of one or more components selected from the group consisting offree NBPT, free formaldehyde, free urea, free urea-formaldehyde products(e.g., UFP), catalyst (e.g., MAP, DAP, or MAS), impurities (e.g.,arising from the grade of reactants used), solvent, water, andcombinations thereof. The relative amounts of such components can vary,with exemplary amounts and ratios disclosed below.

The reaction products disclosed herein can include widely varying molepercentages of urea, formaldehyde, and NBPT (including complexed andfree forms of each component, e.g., as determined by elementalanalysis). Similarly, the reaction products disclosed herein can havewidely varying molar ratios, particularly as the method of producing theadduct-containing compositions can vary. In some specific embodiments,the reaction products can have a molar ratio of about 1:0.5 to about 1:2NBPT:urea (including complexed and free forms of each component, e.g.,as determined by elemental analysis). In certain embodiments, urea isused in great excess with respect to the NBPT; consequently, in suchembodiments, the molar ratio of NBPT:urea is significantly lower. Insome specific embodiments, the reaction products can have a molar ratioof about 1:0.5 to about 1:2 NBPT:formaldehyde (including complexed andfree forms of each component, e.g., as determined by elementalanalysis). Again, in some embodiments, the formaldehyde is present insignificant excess with respect to the NBPT and, in such embodiments,the molar ratio of NBPT:formaldehyde is significantly lower.

The reaction products disclosed herein can advantageously exhibiteffective urease inhibition and, in preferred embodiments, can exhibitslow release of NBPT, providing extended urease inhibition properties.Accordingly, the urease inhibition exhibited by these reaction productscan be achieved over a longer period of time than that exhibited by acomparable composition comprising only free (i.e., unreacted) NBPT.Surprisingly, the reaction products, in some embodiments, can exhibiteffective urease inhibition even at NBPT levels that have beenestablished as ineffective. In other words, a reaction product preparedusing a given amount of NBPT can, in some embodiments, exhibit effectiveurease inhibition even where a comparable composition comprising thatsame amount of NBPT in free (i.e., unreacted) form does not showsignificant urease

The reaction product obtained according to the methods disclosed hereincan be used or stored for later use in the form in which it is provided,can be treated in some manner before being used or stored for later use(e.g., to provide it in a different form or to isolate one or morecomponents therefrom), and/or can be combined with other componentsbefore being used or stored for later use. Various compositionscomprising at least a portion of the reaction products disclosed hereinare disclosed herein below.

For example, in one embodiment, the reaction product is maintainedsubstantially in the form in which it is provided following reaction(e.g., in undiluted liquid or solid form, in solution form, insuspension/dispersion form, in the form of urea-based granulescomprising the adduct, and the like). As noted above, such forms can, insome embodiments, comprise other components, e.g., residual reactantsand/or solvent. The specific form of these as-formed reaction productsmay, in certain embodiments, be further modified prior to use and/orstorage, e.g., by concentrating solution or suspension/dispersion formsby removing solvent therefrom, by diluting any of the forms by addingone or more solvents thereto, by solubilizing solid forms, or bycontacting a solid, undiluted liquid, solution, or suspension/dispersionform with a solid support so as to provide the reaction product in solidform. In one particular embodiment, the reaction product is provided inhomogenous solution form.

In another embodiment, the reaction product is treated so as to isolateone or more adducts therefrom. For example, the reaction product can betreated so as to remove any or all components other than the adductsfrom the reaction product to obtain a mixture comprising all adducts, amixture comprising some adducts, or one or more single, isolatedadducts. Such isolated mixtures or single adducts can be provided intheir natural forms (e.g., in solid or liquid, substantially pure form)or can be treated as described with regard to the as-formed reactionproducts modified prior to use or storage (e.g., to provide a solutionor suspension/dispersion of the adduct or adducts by adding one or moresolvents thereto, or to provide an adduct or adduct mixture in solidform by contacting the adduct or adduct mixture in solid, undilutedliquid, solution, or suspension/dispersion form with a solid support).

In a further embodiment, the reaction product (as-formed, or modified asnoted above) or the isolated adduct(s) (as-provided, or modified asnoted above) can be combined with one or more other components. Forexample, certain compositions are provided which comprise the reactionproduct admixed with one or more other components, e.g., one or morenitrogen sources (e.g., urea or a urea formaldehyde product) or freeNBPT. Certain compositions are provided which comprise the one or moreisolated adducts admixed with one or more other components, e.g., one ormore nitrogen sources (e.g., urea or a urea formaldehyde product) orfree NBPT. Again, any of these combinations can be in varying forms(e.g., in solid form, undiluted liquid form, solution form,dispersion/suspension form, and the like).

As-Formed Reaction Product

As described in detail above, the reaction products provided herein cancomprise varying amounts of adduct(s) and can further comprise varyingamounts of other components. The particular makeup of the reactionproduct can determine the methods of use for which that reaction productis particularly suited.

For example, where a reaction product is provided that comprises asignificant free urea content and/or a significant urea-formaldehydeproduct content, the reaction product (in varying physical forms, e.g.,as described above) can be employed as a fertilizer composition. Forexample, although not intending to be limited, reaction productscomprising at least about 90% urea, at least about 95% urea, at leastabout 98% urea, or at least about 99% urea can be used as fertilizercompositions. As the reaction products can contain varying amounts ofurea and/or urea-formaldehyde product, the amount of the reactionproduct to be applied as a fertilizer composition can vary accordingly.The rate at which such compositions are applied to soil may, in someembodiments, be identical to the rate at which urea is currently usedfor a given application or can be scaled accordingly (e.g., based on theweight percent of urea contained within the reaction product).

A reaction product comprising a high concentration of urea can broadlybe used in all agricultural applications in which urea is currentlyused. These applications include a very wide range of crop and turfspecies, tillage systems, and fertilizer placement methods. Thecompositions disclosed herein are useful for fertilizing a wide varietyof seeds and plants, including seeds used to grow crops for humanconsumption, for silage, or for other agricultural uses. Indeed,virtually any seed or plant can be treated in accordance with thepresent invention using the compositions of the present invention, suchas cereals, vegetables, ornamentals, conifers, coffee, turf grasses,forages and fruits, including citrus. Plants that can be treated includegrains such as barley, oats and corn, sunflower, sugar beets, rape,safflower, flax, canary grass, tomatoes, cotton seed, peanuts, soybean,wheat, rice, alfalfa, sorghum, bean, sugar cane, broccoli, cabbage andcarrot. Application of a reaction product containing a significant ureaconcentration to soil and/or plants can increase the nitrogen uptake byplants, enhance crop yields, and minimize the loss of nitrogen from thesoil.

Such reaction products can be useful in fertilizing and inhibitingurease in various types of soils. Although not limited thereto, suchcompositions in certain embodiments, find particular use in very acidicsoil. It is generally understood that acidic soil degrades NBPT;however, the presently disclosed reaction products have been shown toperform well in acidic soil (e.g., better than urea-based fertilizercombined with an equivalent amount of free NBPT).

In some embodiments, the reaction product is used (in varying forms,e.g., as described above, including in isolated adduct form) incombination with one or more fertilizer compositions. Such methods areapplicable both for reaction products comprising a significant ureaconcentration and reaction products comprising a lower ureaconcentration (including reaction products comprising little to no freeurea). For example, the reaction product can be applied to the soilbefore, concurrently with, or after application of a nitrogen-basedfertilizer composition. The reaction product can be combined with thefertilizer composition, e.g., within the soil, on or about the surfaceof the soil, or a combination thereof. The urea can include any of thetypes of urea disclosed hereinabove, such as free urea,urea-formaldehyde products, and the like and additionally can includevarious substituted ureas. Another suitable urea source can be or caninclude animal waste(s) such as urine and/or manure produced by one ormore animals, e.g., cows, sheep, chickens, buffalo, turkeys, goats,pigs, horses, and the like.

In some embodiments, the urea source can be or can include animal wastesuch as urine and/or manure deposited on and/or in the soil or thenitrogen source can be or can include a fertilizer product previouslyapplied to the soil. As such, the reaction product can be applied to thesoil and mixed with the animal waste and/or previously appliedfertilizer(s) on the surface of and/or within the soil. The reactionproduct can be applied to the soil before, during, and/or after theanimal waste and/or fertilizer(s) are deposited on/in the soil. Inanother example, the urea source can be or can include animal waste suchas urine and/or manure that can be collected and placed within a holdingtank, pond, or the like, and the reaction product can be added to theanimal waste to provide a mixture. The resulting mixture can then bedeposited about the soil to act as a fertilizer therein.

Reaction Product+Free NBPT

In certain embodiments, the reaction product (in varying forms, e.g., asdescribed above, including in isolated adduct form) can be combined withadditional free urease inhibitor (e.g., including, but not limited to,additional free NBPT). The reaction product and free urease inhibitorcan, in some embodiments, be combined during use (e.g., the reactionproduct can be applied to the soil before, concurrently with, or afterapplication of free NBPT).

In certain embodiments, the reaction product and free urease inhibitorcan be provided within a single composition. The free urease inhibitorcombined with the reaction product can be the same urease inhibitor or adifferent urease inhibitor than that present in the adduct or can be acombination of the same urease inhibitor and a different ureaseinhibitor. In such compositions, the free urease inhibitor (e.g., NBPT)can be present in varying amounts. The adduct and free urease inhibitorcan be provided in roughly equivalent amounts, the amount of NBPT may begreater than the amount of adduct, or the amount of NBPT may be lessthan the amount of adduct. In some embodiments, the molar ratio ofNBPT:adduct is between about 1:1 and about 1:10, e.g., between about 1:1and about 1:7. In other embodiments, the molar ratio may be betweenabout 10:1 and about 1:1, e.g., between about 7:1 and about 1:1. Inother embodiments, the weight ratio of adduct to free NBPT product is inthe range from about 4:1 to 1:4 (as measured by phosphorous content),including 3:1 to 1:3, 2:1 to 1:2, and a 1:1. Such embodiments caninclude a solution of adduct and free NBPT, or a fertilizer (solid ormolten) comprising adduct and free NBPT. A solution of adduct and freeNBPT may contain between about 15 wt. % in total of adduct and free NBPTto about 50 wt. % in total of adduct and free NBPT, including about 20wt. % in total of adduct and free NBPT to about 40 wt. % in total ofadduct and free NBPT, and about 25 wt. % in total of adduct and freeNBPT to about 30 wt. % in total of adduct and free NBPT.

As noted above, the reaction product disclosed herein may, in someembodiments, already contain some percentage of free (unreacted) NBPT,which was added to the reaction mixture (but which did not react underthe reaction conditions to form an adduct). Accordingly, in someembodiments, free NBPT can be added to the reaction product to bring thetotal amount of free NBPT to within the desired range. In otherembodiments (e.g., wherein the reaction product is in the form ofisolated adduct form), little to no NBPT is understood to be present inthe isolated single adducts or mixtures thereof; accordingly, sufficientfree NBPT must be added to bring the free NBPT content of the resultingcomposition within the ranges referenced above.

Surprisingly, the adducts disclosed herein in combination with free NBPTcan, in some embodiments, exhibit synergistic activity. For example,when a reaction product is combined with free NBPT, the resultingcomposition can exhibit greater urease inhibition than would be expectedbased on the urease inhibition of a comparable amount of NBPT, all infree (unreacted) form, or than would be expected based on the ureaseinhibition of a comparable amount of adducts alone.

In certain embodiments, the reaction product/free NBPT compositions canbe directly employed as fertilizer compositions (i.e., where thereaction product comprises a significant free urea content and/or asignificant urea-formaldehyde product content). However, more commonly,such reaction product/free NBPT compositions are used in combinationwith a nitrogen source. In such embodiments, a composition comprisingthe reaction product and free NBPT can be applied in varying forms(e.g., in liquid, solution, dispersion/suspension, or solid form) to thesoil before, concurrently with, or after application of a nitrogen-basedfertilizer composition. The nitrogen-based fertilizer can include, forexample, any of the types of urea and urea-formaldehyde productsdisclosed hereinabove. The composition can be combined with thefertilizer composition, e.g., within the soil, on or about the surfaceof the soil, or a combination thereof. The reaction product/free NBPTcomposition advantageously provides effective urease inhibition withregard to the nitrogen-based fertilizer composition.

Reaction Product+Urea

The reaction product can, in some embodiments, be combined with anitrogen source to provide an adduct-containing fertilizer composition.For example, the reaction product (in various forms, including isolatedadduct form) can, in some embodiments, be combined (e.g., mixed,blended, or otherwise combined) with one or more nitrogen sources (e.g.,urea or urea-formaldehyde products). The relative amounts of adduct andurea in such a fertilizer composition can vary, and in certainembodiments, the amount of adduct can be, for example, within the rangeof about 1 ppm to about 10,000 ppm adduct in the fertilizer composition,including about 20 ppm to about 1000 ppm, and about 100 ppm to about 800ppm. Additionally, the amount of adduct in the fertilizer can bemeasured on a phosphorous basis (i.e. ppmP from the adducts), andincludes the ranges of about 20 ppmP to about 1000 ppmP, 50 ppmP toabout 500 ppmP, and 20 ppmP to 250 ppmP. A composition provided bycombining the reaction product with urea can provide a fertilizercomposition comprising up to about 95% by weight urea, up to about 98%by weight urea, up to about 99% by weight urea, up to about 99.5% byweight urea or up to about 99.9% by weight urea, e.g., between about 95%and about 99.9% by weight urea, between about 98% and about 99.9% byweight urea, or between about 99% and about 99.9% by weight urea, andthe like.

In certain embodiments, the reaction product can be blended directlywith granulated urea or can be used as an additive to liquid (molten)urea. The combining of reaction product with urea can be done at ambienttemperature or at elevated temperature, e.g., at least about 50° C., atleast about 60° C., at least about 70° C., at least about 80° C., atleast about 90° C., or at least about 100° C., such as about 20° C. toabout 150° C. Advantageously, in some embodiments, the reaction productcan be combined with urea under conditions of conventional ureamanufacturing generally including temperatures at which urea is inmolten form, e.g., temperatures of about 130° C. to about 135° C. Insuch embodiments, it is beneficial to ensure that sufficient mixing isemployed during this combining step so that the adduct is substantiallyhomogeneously distributed within the molten urea, particularly beforethe urea melt cools and solidifies in the subsequent granulation step.

The reaction product can be combined with the urea in various forms,e.g., in liquid form, as a solution or suspension/dispersion, or insolid form. The amount of reaction product added to urea in accordancewith this embodiment depends on the desired adduct content of theresulting fertilizer composition and on the adduct content of thereaction product, and can be readily calculated by those skilled in theart. It is noted that, in some embodiment, additional free NBPT can beadded to the reaction product, the urea, or the combination thereof.Other components may be present in the adduct-containing fertilizercomposition, which can be intentionally added or which can be inherentlypresent in one or more of the composition components. For example, thecompositions can comprise, in addition to the urea and reaction productcomponents, some moisture, urea synthesis byproducts, solvent(s), and asnoted further herein, may optionally contain other additives, such asdye(s), NBPT stabilizer(s), and/or micronutrient(s).

Other Optional Components (Applicable to All Compositions DisclosedHerein)

Other optional components may be used in compositions of the presentinvention. Examples of other such components include but are not limitedto: nitrification inhibitors; conditioners; xanthan gum; calciumcarbonate (agricultural lime) in its various forms for adding weightand/or raising the pH of acidic soils; met al containing compounds andminerals such as gypsum, metal silicates, and chelates of variousmicronutrient metals such as iron, zinc and manganese; talc; elementalsulfur; activated carbon, which may act as a “safener” to protectagainst potentially harmful chemicals in the soil; plant protectants;nutrients; nutrient stabilizers; super absorbent polymers; wickingagents; wetting agents; plant stimulants to accelerate growth; inorganicnitrogen, phosphorus, potassium (N—P—K) type fertilizers; sources ofphosphorus; sources of potassium; organic fertilizers; surfactants, suchas alkylaryl polyether alcohols; initiators; stabilizers; cross linkers;antioxidants; UV stabilizers; reducing agents; dyes, such as blue dye(FD & C blue #1); pesticides; herbicides; fungicides; and plasticizers.The content of the additional component(s) disclosed herein can be fromabout 1 to about 75 percent by weight of the composition and depends, inpart, on the desired function of the additional component(s) and themakeup of the composition to which the additional component(s) areadded.

Examples of conditioners include but are not limited to tricalciumphosphate, sodium bicarbonate, sodium ferricyanide, potassiumferricyanide, bone phosphate, sodium silicate, silicon dioxide, calciumsilicate, talcum powder, bentonite, calcium aluminum silicate, stearicacid, and polyacrylate powder. Examples of plant protectants andnutrient stabilizers include silicon dioxide and the like. Examples ofnutrients include, but are not limited to, phosphorus and potassiumbased nutrients. A commercially available fertilizer nutrient caninclude, for example, K-Fol 0-40-53, which is a solution that contains40 wt. % phosphate and 53 wt. % potassium, which is manufactured anddistributed by GBS Biosciences, LLC.

Nitrification inhibitors are compounds which inhibit the conversion ofammonium to nitrate and reduce nitrogen losses in the soil. Examples ofnitrification inhibitors include, but are not limited to, dicyandiamide(DCD), and the like. Although the compositions disclosed herein caninclude DCD, in certain embodiments, the compositions are substantiallyfree of DCD. “Substantially free” means that either no DCD can bedetected in the mixture or, if DCD can be detected, it is (1) present in<1% w/w (preferably, <0.85% w/w, <0.80% w/w, or <0.75% w/w); and (2)does not produce effects characteristic of DCD at higher proportions.For example, a composition substantially free of DCD would not producethe environmental effects of exposure to concentrated or pure DCD evenif a trace amount of DCD could be detected in the mixture. Certainexemplary compositions can have a DCD content of less than about 0.85%by weight, less than about 0.80% by weight, less than about 0.75% byweight, less than about 0.5% by weight, or less than about 0.25% byweight.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific embodiments, they are not to be viewed aslimiting the invention in any specific respect. All parts, proportions,and percentages are by weight unless otherwise indicated.

Example 1 Synthetic Preparation of Adducts

As a representative example, to a solution of NBPT (5.0 g, 29.90 mmol)in N-methylpyrrolidone (NMP, 25 mL), was added to ACS-grade urea (1.79g, 29.90 mmol, 1 equiv), followed by formalin (50%, 795 μL, 29.90 mmol,1 equiv) at room temperature. The reaction mixture was stirred for 24 h.A homogeneous solution was obtained, containing ˜10% unreacted NBPT (asevaluated by HPLC) and adducts, among other species.

TABLE 1 Adduct Formation Observed With Different Reactants and ReactionConditions Reaction Conditions Concentration Reaction NBPT Run of NBPTTemp Time conversion # Reactants (wt. %) Solvent (° C.) (hrs) (%, HPLC)1 NBPT + HCHO 15 water 25° C. 24 82 37% + ACS-U^(a) (1:1:1) 2 NBPT + 13water 25° C. 24 98.9 dimethylolurea (1:1) 3 NBPT + 13 water 25° C. 14499.9 dimethylolurea (1:1) 4 NBPT + 13 water 40° C. 24 96 dimethylolurea(1:1) 5 NBPT + 9 water 40° C. 24 99.2 dimethylolurea (1:4) 6 NBPT +reg-U^(b) 0.027 water 25° C. 24 <1 7 NBPT + reg-U^(b) 0.027 water 25° C.24 26 (MAP added as catalyst) 8 NBPT + HCHO 15 NMP 25° C. 24 67 50% +ACS-U^(a) (1:0.5:1) 9 NBPT + HCHO 15 propylene 25° C. 24 40 50% +ACS-U^(a) glycol (1:0.5:1) 10 NBPT + HCHO 15 propylene 25° C. 24 5550% + ACS-U^(a) carbonate (1:0.5:1) 11 NBPT + HCHO 15 acetonitrile 25°C. 24 33 50% + ACS-U^(a) (1:0.5:1) 12 NBPT + HCHO 14 NMP 25° C. 24 98.750% + ACS-U^(a) (1:1:2) 13 NBPT + HCHO 13 NMP 25° C. 24 98.7 50% +ACS-U^(a) (1:2:2) 14 NBPT + HCHO 15 NMP 25° C. 24 90 50% + ACS-U^(a)(1:1:1) 15 NBPT + HCHO 40 NMP 25° C. 24 91 50% + ACS-U^(a) (1:1:1) 16NBPT + HCHO 55 NMP 25° C. 24 92 50% + ACS-U^(a) (1:1:1) 17 NBPT + HCHO15 NMP 40° C. 24 79 50% + ACS-U^(a) (1:1:1) 18 NBPT + urea 50 none 25°C. 24 80 formaldehyde concentrate (1:1) 19 NBPT + urea 33 NMP 25° C. 2495 formaldehyde concentrate (1:1) 20 NBPT + urea 25 NMP 25° C. 24 99formaldehyde (MAP added concentrate (1:1) as catalyst) 21 NBPT + urea 25NMP/potassi- 25° C. 24 99.9 formaldehyde um phosphate concentrate (1:1)buffer pH 7 22 NBPT + urea 13 NMP 25° C. 24 99.7 formaldehydeconcentrate (1:4) 23 NBPT + urea 33 NMP 40° C. 24 ~100 formaldehydeconcentrate (1:1) ^(a)ACS-U is ACS-grade urea, which is determined asbeing formaldehyde and/or UF free. ^(b)Reg-U is commercial grade ureathat contains approx. 0.4 wt. % formaldehyde as UF.

Example 2 Catalyst Effect

Urea (>99% pure) was treated at 260 ppm with a solution of AGROTAINPRIME (i.e., NBPT-containing solution); note that the formaldehyde isalready present in the urea. After one day, the resulting AGROTAIN®treated urea (ATU) was blended with monoammonium phosphate (MAP) 50:50wt. %, diammonium phosphate (DAP) 50:50 wt. % or ammonium sulfate (AMS)50:50 wt. %. The blends were retained for 6 months and samples wereretrieved for analysis at defined time points. ATU was separated fromthe other blend components prior to analysis by HPLC for NBPT contentand by LC-MS to characterize NBPT and adducts.

TABLE 2 Adduct Formation in the Presence of MAP Free NBPT LC-MS PeakArea Day (HPLC) Free NBPT Adduct 1 Adduct 2 Adduct 3 0 270 1421.5 0 0 01 170 947.9 78.8 0 0 2 120 637.9 202.4 6.4 28.1 3 90 516.7 253.1 8.545.0 4 70 311.8 210.7 8.7 51.8 7 50 219.3 238.2 11.9 74.3 8 40 196.0230.9 9.6 72.2 9 30 207.9 200.7 10.5 73.4 10 30 94.3 145.7 8.4 50.5 1130 129.9 179.3 8.1 71.7 14 20 75.2 128.2 7.8 48.0 16 10 91.5 138.2 8.258.1 18 10 76.9 126.3 8.7 57.7 21 10 51.6 87.3 3.6 39.7 24 10 48.1 93.45.1 43.3 28 8 38.5 84.2 4.5 36.0 31 6 29.7 81.1 2.7 41.3

TABLE 3 Adduct Formation in the Presence of DAP Free NBPT LC-MS PeakArea Day (HPLC) Free NBPT Adduct 1 Adduct 2 Adduct 3 0 270 1421.5 0 0 02 200 882.2 80.6 0 5.5 3 170 795.5 110.8 2.7 8.7 4 150 812.5 189.0 4.818.5 7 140 624.0 240.5 6.5 26.0 8 130 712.8 245.9 5.8 23.7 9 110 454.1238.1 6.5 27.7 10 100 448.0 272.9 7.0 39.2 11 80 563.6 349.0 9.0 49.5 1470 339.6 322.2 8.8 58.0 16 60 239.1 304.4 10.9 63.7 18 60 299.0 365.810.9 68.4 21 50 196.4 377.1 9.8 87.5 24 50 175.1 373.9 14.3 101.8 28 40197.4 395.2 15.8 103.3 31 30 148.9 355.3 16.6 108.0

TABLE 4 Adduct formation in the Presence of AMS Free NBPT LC-MS PeakArea Day (HPLC) Free NBPT Adduct 1 Adduct 2 Adduct 3 0 270 1421.5 0 0 02 200 850.1 74.0 4.4 7.8 3 190 1022.9 124.6 2.7 8.5 4 190 873.5 145.15.3 13.7 7 170 708.9 243.6 6.3 30.5 8 170 740.5 232.3 5.6 29.2 9 150661.9 245.7 7.3 34.6 10 140 871.5 320.7 7.8 45.3 11 140 613.9 233.9 4.932.3 14 120 602.8 288.3 6.5 39.9 16 120 556.3 336.3 9.2 54.1 18 100 632372.8 10.2 59.9 21 110 497.2 367.0 7.8 54.4 24 120 420.1 319.2 8.3 50.828 140 535.8 214.8 7.3 44.5 31 80 479.1 415.0 13.9 80.3

Example 3 Determination of Urease Inhibition

The effectiveness of urease inhibition was measured as follows. One tbspof water was used to moisten 4 oz (˜100 g) of Tifton, GA soil of pH 7.7.The moist soil was placed in an 8 oz plastic cup with a tight-fittinglid. Approximately 1 tsp (˜2 g) of NBPT- and/or adduct-treated ureagranules, was applied to the soil surface and the container was sealed.The container was incubated at room temperature for three days andanalyzed for ammonia volatilization by inserting an ammonia-sensitiveDräger tube through the lid of the sealed container. In this way, theamount of ammonia present in the headspace of the container wasquantified up to 600 ppm, the limit of the Dräger tube. In general, moreeffective urease inhibitors are characterized by having lowerconcentrations of ammonia in the headspace. All tests were run induplicate in the presence of a positive control (i.e., untreated urea),which typically exhibits >600 ppm ammonia after 3 days followingapplication.

Various compositions comprising NBPT and/or the adducts disclosed hereinwere prepared by combining NBPT and/or adducts with urea granules; andurease inhibition was determined using the methodology described above.The adducts used in this example were prepared according to entry 14, inTable 1, above.

The data in FIG. 1 show the effect of various urease inhibitors, namelyNBPT and/or the adducts disclosed herein, on volatilization of ammoniafrom treated urea exposed to soil according to the method outlinedabove. For comparison purposes, the data is presented according to thephosphorous content (i.e. ppmP as measured by ICP), of the variousinhibitors used to treat the urea. These data show that increasing theamount of NBPT with respect to the urea content in the range of 111-196ppmP has no significant effect on the onset of significant ammoniavolatilization. For example, the onset of significant ammoniavolatilization (arbitrarily chosen as ≧100 ppm) is comparable for ureatreated with varying amounts of NBPT at about Day 8 followingapplication, i.e., ATU 111 ppmP=ATU 128 ppmP=ATU 196 ppmP. However, whensome of the NBPT is replaced with the adducts disclosed herein—at thesame phosphorus content—a noticeable delay in the onset of significantammonia volatilization is observed e.g., ≧100 ppm ammonia at no earlierthan Day 9 following application, i.e., ‘NBPT/Adducts 42/69 ppmP’>ATU111 ppmP. Further, when NBPT and the adducts disclosed herein arecombined with urea in a ratio of NBPT:adducts of 1:1 by phosphoruscontent, the onset of significant ammonia volatilization is not observeduntil after Day 10 following application, i.e., ‘NBPT/Adducts 111/85ppmP’>>ATU 196 ppmP. Surprisingly, adducts alone do not outperform anequivalent amount of NBPT, i.e., ‘Adducts 111 ppmP’=ATU 111 ppmP. Thisconfirms the synergistic relationship between NBPT and the adductsdisclosed herein, as described above.

Example 4 Volatilization Analysis

Cumulative N loss through volatilization was determined over a span of14 days for NBPT- and/or adduct-treated urea granules applied to soil ata pH of 5.05. In general, more effective urease inhibitors arecharacterized by having lower production of N. All tests were run induplicate in the presence of a control (i.e., unfertilized soil).

Soil (pH of 5.05) was obtained (representing the surface 4 inches ofsoil from a given location) and the soil was air dried, passed through a2-mm sieve, and homogeneously mixed with a cement mixer. Portions of theair dried soil (500 g each) were transferred to individual jars. Thesoil moisture in each jar was adjusted to ⅔ of water holding capacity byadding deionized water and thoroughly mixing to ensure consistentmoisture throughout the soil within each jar. Once the moisture wasequilibrated throughout the soil, the jars were placed inside atemperature controlled wooden cabinet for 24 h to equilibrate themoistened soil to 26° C. Three N sources were evaluated, including twoexperimental urease inhibitor-treated ureas and untreated urea. Inaddition, an untreated soil was included to evaluate background ammonialevels. The urea for all treatments was passed through an 8-mesh sieveand retained on a 10 mesh sieve to ensure uniformity. Nitrogen sourceswere applied at an equivalent rate of 120 pounds of N per acre based onthe surface area of the soil in the jar. Each treatment was replicated 4times and randomly placed into four separate chambers containing fourjars each.

Air flow rates through the soil chambers were controlled at 1.00 L min⁻¹and temperature was maintained at 26° C. Acid traps containing 100 mL of0.02 M ortho-phosphoric acid were used to capture volatilized NH₃ in theair stream flowing over the soil surface. Acid traps were changed at 24,48, 72, 96, 120, 144, 168, 216, 264, 312, and 336 h (2 wk) afterinitiation of the trial. Acid traps were weighed and the total volume ofsolution was calculated using the density of 0.02 M phosphoric acid at25° C. Ammonical N concentration in the acid traps was determinedcolorimetrically using a Lachat QuickChem Automated Ion Analyzer (LachatInstruments, Loveland, Colo.). The trial was analyzed as a randomizedblock design with four replications (blocks). Each trial was analyzedseparately using analysis of variance (ANOVA) using Proc Mixed in SAS(SAS Institute, 2009). Least significant difference (LSD) meanseparation was used to determine treatment differences in cumulative Ncaptured in acid traps at α=0.05. Maximum loss rates were calculated bydividing the percent NH₃ lost during a sampling interval by the duration(hours) of the sampling intervals.

Table 2, below, provides the results of the study, wherein soil N sourceK1 represents urea treated only with carriers (N-methyl pyrrolidone anda dye), soil N source K2 represents ATU (111 ppmP), and soil N source K3represents adduct-treated urea (adduct/NBPT, 55 ppmP/55 ppmP). Theadduct-treated urea used in this example was prepared according to entry14, in Table 1, above.

TABLE 5 Cumulative N Loss Through Volatilization Cumulative N Loss(mg/kg) Soil N Day Day Day Day Day Day Day Day Day Day Day Day Source 01 2 3 4 5 6 7 9 10 12 14 K1 0.00 1.89^(a) 21.65^(a) 26.18^(a) 28.26^(a)29.50^(a) 30.34^(a) 31.39^(a) 31.72^(a) 32.13^(a) 32.32^(a) 32.38^(a) K20.00 0.02^(b) 1.77^(b) 5.08^(b) 8.02^(b) 10.45^(b) 12.25^(b) 14.13^(b)14.65^(b) 15.27^(b) 15.56^(b) 15.65^(b) K3 0.00 0.02^(b) 0.46^(b)1.50^(b) 3.01^(c) 4.79^(b) 6.73^(b) 9.51^(b) 10.21^(b) 10.99^(b)11.36^(b) 11.47^(b) Unfertilized 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.000.00 0.00 0.00 0.00 Soil LSD 1.000 3.690 3.986 4.824 5.678 6.461 7.6067.871 8.162 8.289 8.326 P = 0.05 Standard 0.000 0.550 2.030 2.193 2.6543.124 3.554 4.184 4.330 4.490 4.560 4.580 deviation CV 0.00 85.66 25.5120.08 20.26 20.95 21.62 22.81 22.96 23.07 23.09 23.10 Replicate F 0.0000.828 1.401 1.789 1.396 0.923 0.596 0.352 0.318 0.292 0.281 0.278Replicate 1.000 0.533 0.345 0.266 0.346 0.494 0.644 0.790 0.813 0.8300.837 0.840 Prob(F) Treatment F 0.00 15.39 136.80 148.02 101.49 68.7448.31 30.40 27.52 24.77 23.65 23.35 Treatment 1.000 0.007 0.000 0.0000.000 0.000 0.001 0.002 0.002 0.003 0.003 0.003 Prob(F) ^(a)Meansfollowed by same letter or symbol do not significantly differ (P = 0.05,LSD) ^(b)Means comparison performed only when AOV Treatment (P(F) issignificant at mean comparison OSL ^(c)Untreated treatment 4 excludedfrom analysis

The data presented in Table 5 clearly shows that the adduct-treated urea(K3) gave significantly less N loss through volatilization than eitherthe urea treated only with carriers (K1) and the ATU (K2) beginning onDay 2 following application to the acidic soil in this study. After 2days, the adduct-treated urea (K3) gave a 98% reduction in N loss ascompared with urea treated only with carriers (K1) and performed 75%better than the ATU (K2). After 14 days, the adduct-treated urea (K3)gave a 65% reduction in N loss as compared with the urea treated onlywith carriers (K1) and performed 25% better than the ATU (K2).Furthermore, maximum N loss by volatilization was delayed by 2-3 daysusing the adduct treated urea (K3) as compared with that exhibited byATU (K2), even in acidic soil (compare K3 day 7 with the equivalent lossof N for K2 on the curve generated from this data in FIG. 2, day 4-5).

1. A composition comprising one or more adducts ofN-(n-butyl)thiophosphoric triamide (NBPT), urea, and formaldehyde,wherein the one or more adducts are represented by the followingstructures:


2. The composition of claim 1, wherein the composition comprisessubstantially no dicyandiamide.
 3. The composition of claim 1, furthercomprising one or more materials selected from the group consisting offree NBPT, free formaldehyde, urea formaldehyde polymer (UFP), water,and combinations thereof.
 4. The composition of claim 1, wherein theurea and formaldehyde are in the form of a urea formaldehyde reactionproduct comprising dimethylolurea.
 5. The composition of claim 1,wherein the composition is a solution comprising the adduct in anorganic solvent.
 6. The composition of claim 1, wherein the compositionis a synergistic mixture of free NBPT and the adduct.
 7. A fertilizercomposition comprising: urea; and the composition of claim
 1. 8. Thefertilizer composition of claim 7, wherein the composition comprisesabout 90% by weight or more urea.
 9. The fertilizer composition of claim7, wherein the composition comprises about 98% by weight or more urea.10. The fertilizer composition of claim 7, wherein the composition ofclaim 1 is present in an amount between 20 ppmP to 1000 ppmP based onthe total weight of the fertilizer composition.
 11. The fertilizercomposition of claim 7 further comprising free NBPT, wherein the weightratio (as measured by phosphorous content) of the composition of claim 1to free NBPT is in the range from 4:1 to 1:4.
 12. A method of forming afertilizer composition, the method comprising combining a fertilizermaterial with the composition of claim
 1. 13. The method of claim 11,wherein the composition of claim 1 is in the form of a solutioncomprising the adduct in an organic solvent.
 14. The method of claim 13,wherein the method comprises mixing the composition of claim 1 withsolid particles of the fertilizer material.
 15. The method of claim 11,wherein the method comprises mixing the composition of claim 1 with amolten stream of the fertilizer material.
 16. The method of claim 15,wherein the molten stream of fertilizer material comprises formaldehydeor reaction products of urea and formaldehyde.
 17. A method of making aurease inhibiting fertilizer, the method comprising combining urea,formaldehyde, and N-(n-butyl)thiophosphoric triamide (NBPT), such thatan excess of urea is present, to form an adduct of NBPT, urea, andformaldehyde represented by the following:

which adduct remains incorporated into the remaining urea.
 18. Themethod of claim 17, wherein the urea and formaldehyde are in the form ofa urea formaldehyde reaction product comprising dimethylolurea.
 19. Acomposition comprising a mixture of an adduct ofN-(n-butyl)thiophosphoric triamide (NBPT), urea, and formaldehyde; andfree NBPT.
 20. The composition of claim 19, wherein the weight ratio (asmeasured by phosphorous content) of the adduct to free NBPT is in therange from 4:1 to 1:4.
 21. The composition of claim 19, wherein theweight ratio (as measured by phosphorous content) of the adduct to freeNBPT is in the range from 2:1 to 1:2.
 22. The composition of claim 19,wherein the weight ratio (as measured by phosphorous content) of theadduct to free NBPT is about 1:1.
 23. The composition of claim 19,wherein the adduct and free NBPT are present in a solution comprising atleast one solvent selected from the group consisting of NMP, glycol,glycol derivatives and protected glycols, acetonitrile, DMSO,alkanolamines, alkylsulfones, monoalcohols, dibasic esters andderivatives thereof, alkylene carbonates, monobasic esters, carboxylicacids, glycol esters.
 24. A fertilizer composition comprising: urea; andthe composition of claim
 19. 25. The composition of claim 24, whereinthe composition of claim 23 is present in an amount from 50 ppmP to 1000ppmP.
 26. The composition of claim 24, wherein the weight ratio (asmeasured by phosphorous content) of the adduct to free NBPT is in therange from 4:1 to 1:4.
 27. The composition of claim 24, wherein theweight ratio (as measured by phosphorous content) of the adduct to freeNBPT is in the range from 2:1 to 1:2.
 28. The composition of claim 24,wherein the weight ratio (as measured by phosphorous content) of theadduct to free NBPT is about 1:1.